EP0435677A2 - Produit fritté composité à base d'alumine-zircone et procédé pour la production de celui-ci - Google Patents

Produit fritté composité à base d'alumine-zircone et procédé pour la production de celui-ci Download PDF

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EP0435677A2
EP0435677A2 EP90314351A EP90314351A EP0435677A2 EP 0435677 A2 EP0435677 A2 EP 0435677A2 EP 90314351 A EP90314351 A EP 90314351A EP 90314351 A EP90314351 A EP 90314351A EP 0435677 A2 EP0435677 A2 EP 0435677A2
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Prior art keywords
alumina
zirconia
sintered product
crystalline phase
composite sintered
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EP0435677A3 (en
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Yoshitaka Kubota
Shigemi Yamamoto
Hiroshi Yamamura
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Tosoh Corp
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Tosoh Corp
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Priority claimed from JP09919790A external-priority patent/JP3198507B2/ja
Priority claimed from JP2100359A external-priority patent/JP2803314B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C04B35/117—Composites
    • C04B35/119—Composites with zirconium oxide

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  • This invention relates to alumina-zirconia composite sintered products having high strength, high toughness and high hardness, a method for making such products and a method for preparing starting powders for the products.
  • Alumina has been conventionally utilized as a ceramic having good heat and abrasion resistances.
  • the hardness of the alumina is as high as 2000 kg/mm in terms of Vickers hardness, the strength is usually approximately 40 kg/mm 2 and may be approximately 80 Kg/mm 2 for the best one.
  • the fracture toughness is about 3 MN/m3/2 and, thus, alumina is so fragile that its application as a structural material utilizing the abrasion resistance is narrowed.
  • the particle size of zirconia dispersed in alumina is controlled to be within a range of from 0.05 to 2.0 ⁇ m, so that tetragonal zirconia particles dispersed in the alumina can be retained at room temperature, resulting in a strength of 76 kg/mm 2 and a toughness of 9.6 MN/m3/2.
  • the alumina ceramics dispersing zirconia therein are unsatisfactory with respect to the strength.
  • alumina ceramics dispersing zirconia From an angle different from the alumina ceramics dispersing zirconia, high-performance ceramics have been developed.
  • This class is directed to ceramics mainly composed of zirconia and is disclosed, for example, in Japanese Unexamined Patent Publication No. 55-140762. More particularly, a co-precipitation technique is utilized wherein oxides of Y, Ca, Mg and the like serving as a stabilizer for zirconia are uniformly added so as to obtain a finer powder. The use of the powder can suppress the stabilizer necessary for ordinary stabilization to half the amount in an ordinary case. By this, ceramics consisting of tetragonal zirconia particles, which are in a metastable phase at room temperature, have been obtained.
  • the tetragonal zirconia particles which are in a metastable phase are transformed into a monoclinic crystal system at the time of fracture, thus leading to high strength.
  • a typical composition of the ceramic is a tetragonal zirconia ceramic to which 3 mol% of yttria is doped and has a strength of 120 kg/mm 2 and a toughness of 6 MN/m 3/2 .
  • the Vickers hardness of the zirconia ceramic is as low as about 1250 kg/mm 2 , which is unsuitable for use as abrasion-resistant, structural ceramics.
  • alumina is added to the ceramics mainly composed of a tetragonal zirconia system. These are disclosed, for example, in Japanese Unexamined Patent Publication Nos. 60-86073 and 58-120571. In these attempts, while the strength and toughness of zirconia are utilized, it is contemplated to improve the hardness and strength by addition of alumina.
  • a composite product of 3 mol% yttria-doped tetragonal zirconia to which 28% by volume of alumina is added is imparted with a strength of 240 kg/mm 2 according to a hot isotactic pressing (HIP) method.
  • HIP hot isotactic pressing
  • cerium oxide is used as the stabilizer, a tetragonal zireonia produced by the action of cerium oxide is very likely to undergo transformation by application of stress, leading to high toughness or tenacity rather than strength.
  • zirconia particles and alumina particles have similar size distributions ; and the fine structure of a composite sintered product obtained from a mixed powder of such particles is not satisfactory because of the poor dispersibility of the alumina and zirconia particles or the tendency that the alumina particles and the zirconia particles are dispersed as independent particles. In short, it is difficult to separately control the sizes of the alumina particles and the zirconia particles.
  • an alumina-zirconia composite sintered product which comprises a zirconia crystalline phase composed mainly of a tetragonal zirconia or zirconia containing not larger than 4 mol% of yttrium oxide or not larger than 14 mol% of cerium oxide and an alumina crystalline phase, the sintered product having such a fine structure that regions of said alumina crystalline phase being separated with the zirconia crystalline phase at a size of 0.1 to 2 ⁇ m on average.
  • a method for preparing an alumina-zirconia composite powder which comprises dispersing a-alumina particles having an average particle size of from 0.1 ⁇ m to 2 ⁇ m in a zirconia sol having a zirconia dispersed phase having an average particle size of not larger than 0.1 ⁇ m, subjecting the resulting mixed dispersion to dehydration to obtain a dried matter, and calcining the dried matter to obtain a mixed powder of crystalline zirconia particles and the a-alumina particles.
  • a method for making an alumina-zirconia composite sintered product comprising shaping the mixed powder obtained by the above method and sintering the shaped powder to obtain an alumina-zirconia composite sintered product.
  • the composite sintered product may be obtained without subjecting any stabilizer to solid solution in a zirconia crystalline phase but when either yttrium oxide or cerium oxide is incorporated in the zirconia crystalline phase, a sintered product having higher strength is obtained.
  • the amount of the stabilizer in the zirconia crystalline phase is not larger than 4 mol% for yttrium oxide and not larger than 14 mol% for cerium oxide. Over these ranges, the transformation effect decreases with a increase of the stability of tetragonal zirconia, with result that a final sintered product does not have high strength and high toughness.
  • the content of alumina is generally in the range of from 40 to 90% by volume. If the content is less than 40% by volume, the hardness of the resultant composite sintered product is as low as 1450 kg/mm 2 , which is not significantly higher than those of a product consisting of a zirconia crystalline phase alone . On the other hand, over 90% by volume, it becomes difficult to make such a fine structure necessary for showing high strength and high toughness.
  • the content of alumina is increased.
  • the content of yttrium oxide or cerium oxide in zirconia is decreased, so that the stability of zirconia is lowered, with a tendency toward transformation, by which the reduction in the effect of the transformation is compensated.
  • the lowering in the stability of the tetragonal zirconia by reduction in amount of the stabilizer can be prevented by an increase in amount of alumina.
  • the content of the alumina crystalline phase in the composite sintered product should be not less than about 50% by volume, preferably not less than 65% by volume.
  • alumina should be contained in an amount of not less than about 70% by volume.
  • an average size of regions of the alumina phase surrounded by the zirconia crystalline phase there are upper and lower limits.
  • the upper size should preferably be decreased from not larger than 2 ⁇ m to not larger than 0.6 ⁇ m with a decrease in content of yttrium oxide as is particularly shown in Fig. 2.
  • the upper limit of the average size of regions of the alumina phase surrounded by the zirconia crystals should preferably be decreased from not larger than 2 ⁇ m to not larger than 1 ⁇ m with a decrease in content of cerium oxide as is particularly shown in Fig. 4.
  • the tetragonal zirconia in the zirconia crystal phase of a composite sintered product should preferably be not less than 70% by volume.
  • Fig. 5 shows a microphotograph in section of a composite sintered product having an alumina content of 70% by volume, revealing such a structure wherein the alumina crystalline phase (black) is uniformly dispersed in the zirconia crystalline phase (white) and is surrounded by the zirconia phase.
  • the sintered product of the invention having a fine structure wherein the zirconia phase uniformly surrounds the alumina crystalline phase can be obtained by uniformly dispersing the alumina particles in zirconia while suppressing the grain growth of the particles.
  • the uniformity may be evaluated by scattering of comparisons of the ratio by volume of the zirconia crystalline phase and the alumina crystalline phase in a region with a given area with an average composition in a composite sintered product.
  • the area of the given region may be determined as a ratio in area between zirconia and alumina in a rectangular area which has a size of 10 times an average size of alumina phase region. This can be measured by means of an X-ray microanalyzer.
  • the fine structure of the invention wherein particles of the alumina crystalline phase are dispersed in the zirconia crystalline phase may be defined such that the scattering is within 20%, preferably within 10%, of the average composition.
  • the hardness of the composite material is controlled by the content of alumina, i.e. the hardness increases substantially linearly as the content is increased.
  • alumina in general, in order to obtain a Vickers hardness of not lower than 1500 kg/mm 2 , it is necessary to add alumina in an amount of not less than 45% by volume.
  • yttrium oxide When yttrium oxide is used as a stabilizer, conditions necessary for achieving a strength of not less than 140 kg/mm 2 , a fracture toughness of not less than 4 MN/m 3/2 and a Vickers hardness of not less than 1500 kglmm , are that the contents of yttrium oxide, zirconia and alumina are defined within a range on the lines obtained by connecting points A(45, 3.0)-B(45, 1.5)-C(85, 0.5)-D(85, 1.5)-E(54, 3.0)-A(45, 3.0) of Fig. 1 (i.e.
  • a content of alumina in a sintered product (% by volume) and a size of the region of the alumina crystalline phase (pm)) and surrounded by the lines, and the average size of regions of the alumina crystalline phase is defined within a range on or surrounded by the above lines, there can be obtained characteristics including a strength of not less than 160 kg/mm 2 , a fracture toughness of not less than 5 MN/m 3/2 and a Vickers hardness of not less than 1600 kg/mm 2 .
  • cerium oxide When cerium oxide is used as a stabilizer, the necessary conditions for achieving a strength of not less than 100 kg/mm 2 , a fracture toughness of not less than 4 MN/m 3/2 and a Vickers hardness of not less than 1400 kg/mm 2 , the contents of cerium oxide, zirconia and alumina are defined within a range on the lines obtained by connecting points 1(50, 14)-J(50, 8)-K(90, 4.5)-L(90, 7)M(70, 13)-l(50, 14) of Fig.
  • the strength of the sintered product set forth above is liable to suffer an influence of defects in the inside or cracks produced by surface processing. If these defects or cracks are present, such a strength as stated above may not always be obtained.
  • the sintered product containing tetragonal zirconia may have a residual stress strongly left in the surface thereof when subjected to a surface processing method. In this case, the development of cracks which are produced by means of a Vickers indenter is suppressed by the residual surface stress and its length becomes short. Accordingly, the value of the fracture toughness may be evaluated as larger.
  • the dispersion medium of a mixed dispersion wherein crystalline alumina particles having an average par- tide size of from 0.1 ⁇ m to 2 ⁇ m are dispersed in a zirconia sol having a zirconia dispersed phase having an average size of not larger than 0.1 ⁇ m, is water or an aqueous solution of an organic solvent, or an aqueous solution dissolving a salt of yttrium, calcium, magnesium, cerium or the like, which is converted to a stabilizer for zirconia by calcination.
  • the organic solvents include alcohols having from 1 to 9 carbon atoms, acetone and the like.
  • the zirconia dispersed system which is one of the dispsersed phases is colloid particles called hydrous zirconia or zirconium hydroxide, respectively.
  • the particles are crystalline or amorphous and are ones which are confirmed as having a monoclinic structure according to the Raman spectroscopy. These particles are made of single or coagulated particles.
  • the average particle size should be not larger than 0.1 pm. Over 0.1 ⁇ m, they are liable to precipitate in a solution with a lowering in dispersability with alumina.
  • the starting alumina used in the present invention is a-alumina particles. If other types of alumina particles are used, the crystal form will be changed at the time of firing or sintering, making it difficult to control the particle size and preventing the resultant sintered product form being densified.
  • the average particle size should be within a range of from 0.1 pm to 2.0 pm. If the size is below this range, the resultant sintered product becomes low in fracture toughness. On the other hand, over the range, the strength is lowered with a lowering of sinterability.
  • the mixed dispersion can be prepared in the following manner.
  • Alumina particles are dispersed in the zirconia sol to obtain the mixed dispersion.
  • the zirconia sol may be either a commercially available sol or a sol which is obtained by subjecting an aqueous solution of a water-soluble zirconium salt such as zirconium oxychloride to hydrolysis or neutralization by a usual manner, provided that the zirconia dispersed system has an average particle size of not larger than 0.1 ⁇ m. In the latter case, in order to remove residual chlorine, an ion exchange resin may be used for dechlorination.
  • water-soluble salts such as chlorides or nitrates of yttrium, magnesium, calcium, cerium and the like are added to the above-stated commercially available zirconia sol or the zirconia sol obtained from an aqueous solution of a zirconium salt, or to the aqueous solution of a zirconium salt.
  • an a-alumina powder is added to the resultant solution and usually dispersed by the use of a powdering or mixing machine such as a ball mill.
  • the particle size of the alumina powder greatly influences the size of the alumina regions in a final composite sintered product.
  • the alumina powder used should have a size which is equal to or smaller than the region size. This is because there is the tendency that owing to the growth of the alumina powder during the sintering or the insufficient dispersion of the alumina particles in the mixed powder, the alumina region size becomes, more or less, larger than the size of the alumina powder. In some case, the size may become smaller owing to the breakage into fine pieces prior to the sintering.
  • Organic solvents such as an alcohol or acetone may be added for preventing the particles from coagulation during the course of drying.
  • the mixed solution where the zirconia dispersing medium and the a-alumina particles are sufficiently dispersed is dried by evaporation to dryness or dehydration under reduced pressure.
  • the resultant dried matter is generally calcined in air at 500°C to 1300°C.
  • the calcination is performed at 700 to 1200°C for about 2 hours in air. If the calcination temperature is lower than 500°C, not only the crystallization of zirconia does not proceed satisfactorily, but also moisture or organic matters which have not been removed by the drying cannot be fully removed. On the contrary, over 1300°C, crystalline zirconia particles in the powder become too great, resulting in a lowering of sinterability.
  • the crystalline zirconia particles grow to such an extent that its size is larger than that of the a-alumina particles, it becomes difficult to provide a fine structure of a final composite product wherein the crystalline zirconia phase surrounds a-alumina regions therewith. In this case, all the strength, fracture toughness and hardness cannot be improved.
  • the specific surface area of the crystalline zirconia particles is kept at a level of not less than about 1.5 times that of the a-alumina particles.
  • the specific surface area of zirconia in the mixed powder can be calculated as 35 m 2 /g, from which the average particle size can be calculated as about 15 nm.
  • the state of the composite powder of the invention is an important factor on which the fine structure of the sintered product is determined.
  • the composite powder of the invention is a mixture of a fine zirconia powder and an alumina powder having a larger average particle size. According to the method of the invention, there can be obtained a mixed powder containing zirconia particles having a specific surface area of not less than 10 m 2 /g.
  • the average particle size of the alumina in the mixed powder is arranged in the range of from 0.1 to 2.0 ⁇ m, preferably from 0.1 to 1.6 11m.
  • the mixed powder of the invention is obtained.
  • the powder is subsequently subjected to powdering of coagulated particles by the use of a milling machine such as a ball mill or a dispersing machine such as of ultrasonic waves, thereby obtaining a powder for sintering according to the invention.
  • a sintered product from the thus obtained mixed powder there is obtained a shaped green body by a usual method such as press molding, hydrostatic molding using a rubber mold, cast molding, injection molding or the like.
  • the green body is sintered in an ordinary electric furnace in air at a temperature ranging from 1200°C to 1600°C.
  • the sintering temperature greatly influences the characteristics of the sintered product. Over 1600°C, the particle size of zirconia becomes large with the tendency toward transformation of the tetragonal system zirconia, resulting in a high fracture toughness but a lowering of strength.
  • the temperature is in the range of from 1200 to 1600°C, preferably from 1350 to 1550°C.
  • the sintering is continued at a temperature of not lower than 1300°C for 2 hours, the water absorption of the sintered product becomes substantially zero. If the product is subsequently subjected to hot isotactic pressing treatment as will be described hereinbelow, voids can be removed by the treatment, showing a better effect of improving the strength of the sintered product.
  • the hot isotactic pressing treatment should preferably be effected.
  • the treating conditions generally include a pressure of not less than 500 kg/cm 2 , a temperature of from 1200°C to 1600°C, preferably from 1350°C to 1550°C.
  • the temperature is preferably effected at a level equal to or lower than the sintering temperature.
  • the treating gas is an inert gas or an oxygen-containing inert gas.
  • the sintered product obtained after the HIP treatment is substantially free of any void with a remarkably improved strength.
  • the composite sintered product of the invention has a large content of alumina.
  • the product At a compositional ratio which is assumed as dispersing zirconia in alumina, the product has such a structure where alumina is dispersed in zirconia. In this condition, the alumina is particles that are separated from one another substantially as independent particles in a zirconia crystalline phase.
  • the composite sintered product having such a structure as stated above is broken down, cracks predominantly develop along or in the crystalline layers of zirconia, so that the transformation effect of the dispersed zirconia can be utilized to a maximum. Accordingly, even in a composition where a very large amount of alumina is contained, the toughening mechanism of zirconia acts effectively. While keeping the high strength and high toughness inherent in the zirconia ceramics, the high hardness of alumina is achieved. Thus, the composite sintered product of the invention shows its effect owing to its specific type of fine structure.
  • colloidal zirconia particles are used as a starting material for zirconia.
  • the zirconia colloid particles are dispersed in a solution without coagulation although they are fine.
  • alumina particles are far large in size.
  • the composite powder has such a structure that the individual alumina particles are sufficiently surrounded by fine zirconia particles.
  • the resultant product has a structure where alumina particles are dispersed in zirconia even when using a composition comprising not less than 50% by volume of alumina. In this condition, a fine structure is likely to form wherein alumina regions are substantially independently separated with zirconia crystalline phases.
  • the composite sintered product of the present invention has well-balanced high strength, high toughness and high hardness. Especially, with a product which is obtained using yttrium oxide as a stabilizer and and which is free of any internal defect by the HIP treatment, it has a strength of204 kg/mm 2 , a fracture toughness of 5.9 MN/m-"2 and a Vickers hardness of 1760 kg/mm 2 . Any known alumina-zirconia composite sintered product has never been known as having such good characteristics as mentioned above.
  • HIP treatment is not effected, there are obtained good characteristics including a strength of not less than 100 kg/mm 2 , a fracture toughness of not less than 4 MN/m3/2 and a Vickers hardness of not less than 1500 kg/mm 2 .
  • the alumina-yttrium oxide-containing zirconia composite sintered product and the alumina-cerium oxide-containing zirconia composite sintered product have a strength of not less than 100 kg/mm 2 with a very small scattering of measured values. Especially, with cerium oxide-containing composite sintered products, the scattering is very small. In examples of the present invention, its standard deviation is, in most case, within about 12% of the average strength, which proves the excellent effect of the present invention.
  • the sintered product containing cerium oxide as a stabilizer does not show any low temperature degradation phenomenon produced in a temperature range of from 200 to 400°C, and this is a difference from the product containing yttrium oxide.
  • the present invention is more particularly described by way of examples.
  • yttrium oxide 1.12 g was dissolved in 150 g of a zirconium oxychloride aqueous solution containing 30 g of zirconium oxide as calculated. The aqueous solution was refluxed at the boiling point for 70 hours to hydrolyze zirconium oxychloride.
  • the zirconia particles had an average size of 15 nm.
  • the thus obtained powder was shaped in a mold and molded by the use of isotactic pressing machine at a pressure of 2 tons/cm 2 .
  • the molding was sintered in an electric furnace at 1500°C for 2 hours to obtain a zirconia-alumina composite sintered product.
  • the water absorption of the sintered product was 0%.
  • the product was subjected to a hot isotactic pressing (HIP) machine under conditions of 1500 atmospheric pressures, 1400°C and 1 hour.
  • the resulting sintered product had 70% by volume of regions of alumina crystals with an average size of 0.5 11m and a zirconia phase containing 2 mol% of yttrium oxide.
  • Table 1 No. 1
  • FIG. 5 A scanning-type electron microphotograph of the fine structure of the composite sintered product is shown in Fig. 5.
  • the section of the composite sintered product was polished to determine a content of alumina in a 5 ⁇ m square region at ten points on the surface according to an X-ray microanalyzer, with the result of a maximum content of 72% by volume and a minimum content of 68% by volume.
  • the powder was shaped in a mold and press-molded by the use of an isotactic pressing machine at a pressure of 2 tons/cm 2 .
  • the resulting molding product was sintered in an electric furnace at 1475°C for 2 hours to obtain a sintered product.
  • the water absorption of the sintered product was 0%.
  • the resultant sintered product (No. in Table 3) was a composite sintered product which had 70% by volume of regions of alumina crystals having an average size of 0.4 ⁇ m and a zirconia layer having 9 mol% of cerium oxide.
  • Table 3 Nos. 2 to 17
  • various compositions, and alumina powder particle sizes are shown along with powder characteristics and physical properties of sintered products obtained under different sintering conditions.
  • Composite sintered products of different compositions and alumina phase region sizes were prepared using, as starting materials, a commercially available zirconia sol aqueous solution (having a concentration of 20 wt% calculated as zirconia), an yttrium oxide powder and an alumina powder.
  • the yttrium oxide was used after dissolution in 2 me of concentrated hydrochloric acid in a necessary amount.
  • the alumina powders used had average sizes of 0.2, 0.4, 0.6 and 1.6 ⁇ m. These powders were used singly or by mixing at given ratios to change the average particle size.
  • Composite powders were prepared in the same manner as in Example 1 after preparation of mixed solutions.
  • the conditions of preparing the powders and the sintered products are shown in Table 4.
  • the HIP pressure was controlled at 1500 atms., and the atmosphere was made of argon.
  • the characteristics of the resultant composite powders and sintered products are shown in Table 4.
  • zirconia powders containing 1,2 and 3 mol% of yttrium oxide and an average size of 0.6 ⁇ m (TZ-1Y, TZ-2Y and TZ-3Y, available from TOSOH CORPORATION), zirconia powders containing 9 and 12 mol% of cerium oxide and an average size of 0.6 ⁇ m, and alumina powders having sizes of 0.2 and 0.4 ⁇ m.
  • the zirconia powders and the alumina powders were weighed in such amounts as to attain intended compositional ratios of zirconia and alumina, followed by mixing and powdering in a ball mill for 40 hours. After completion of the powdering, each mixture was dried and sintered in the same manner as in Examples 1 and 2 (for the case of Table 5 where the column, HIP temperature, is indicated as "-"). Part of the samples were further subjected to the HIP treatment.
  • composition of alumina at ten points each in a 5 ⁇ m square region of the sintered product was 90% by volume at maximum and 46% by volume at minimum when subjected to an X-ray microanalyzer.
  • Strength strength by bending at three points as prescribed in JIS R 1601. The scattering of the strength is indicated by a standard deviation ( ⁇ n-1 ) following the strength.
  • Toughness a micro-indentation method using a Vickers hardness meter was used, in which a load of 20 kg and a load application time of 10 seconds were used.
  • the toughness was calculated according to the following equation. wherein H is a Vickers hardness, a is a length of a diagonal line of a indent, and c is a median length of a crack produced from the tip of the diagonal line.
  • H is a Vickers hardness
  • a is a length of a diagonal line of a indent
  • c a median length of a crack produced from the tip of the diagonal line.
  • the surface of the sample was buffed with diamond abrasive with a size of 3.0 ⁇ m for mirror polishing. Where a residual stress was left on the surface by the polishing step, the crack development was suppressed with the possibility a high fracture toughness was obtained.
  • Hardness a micro Vickers hardness tester was employed using a load of 500 g and a load application time of 10 seconds.
  • Particle size of sintered product a scanning-type electron microscope was used for observation at an acceleration voltage of 25 Kv. The accuracy is approximately ⁇ 0.1 pm.
  • Size of powder a size distribution measuring instrument using a laser beam scattering was employed.
  • Tetragonal system an X-ray diffraction method was used wherein a diffraction line intensity of the tetragonal system were compared with those of other monoclinic or cubic system. The surface being measured was polished with a #400 diamond wheel.
  • compositional analysis of microregions the composition was analyzed through observation with a scanning-type electron microscope and by the use of an X-ray microanalyzer.
  • the invention thus in summary extends to an alumina-zirconia composite sintered product which comprises a zirconia crystalline phase compound mainly of a tetragonal zirconia and an alumina crystalline phase, the said sintered product having a fine structure, such that regions of the said alumina crystalline phase which are separated by the zirconia crystalline phase, have a size of from 0.1 to 2 ⁇ m on average.
  • the invention also extends to an alumina-zirconia composite sintered product which comprises a zirconia crystalline phase compound mainly of a zirconia crystalline phase containing not more than 4 mol% of yttrium oxide or not more than 14 mol% of cerium oxide as a stabilizer and an alumina crystalline phase, the said sintered product having a fine structure such that regions of the said alumina crystalline phase, which are separated by the zirconia crystalline phase, have a size of from 0.1 to 2 gm on average.
  • the content of the alumina crystalline phase is preferably in the range of from 40 to 90% of volume.
  • yttrium oxide is used as a stabilizer, and the contents of the yttrium oxide and alumina lie within the ranges defined by the lines obtained by connecting points A(45, 3.0)-B(45, 1.5)-C(85, 0.5)- D(85, 1.5)-E(54 3.0)-A(45, 3.0) of fig.
  • cerium oxide is used as a stabilizer, and the contents of cerium oxide and alumina lie within the ranges defined by the lines obtained by connecting points 1(50, 14)-J(50, 8)-K(90, 4.5)-L(90, 7)-M(70, 13)-l(50, 14) of Fig. 3 (the content of alumina in a sintered product (% by volume) and the content of cerium oxide in zirconia (mol%)) and the average size of regions of the alumina crystalline phase lie within the ranges defined by the lines obtained by connection points i(50, 1.9)-j(50, 0.2)-k(90, 0.1)-1 (90, 1.0)-i(50, 1.9) of Fig. 4 (the content of alumina in a sintered product (% by volume) and the size of the region of the alumina crystalline phase ( ⁇ m)).
  • the average composition in a fine rectangular region having one side which is ten times an average of the size of the regions of the alumina crystalline phase in the said composite sintered product differs at any portion of the said composite sintered product, by no more than 20% from the average composition of the entirety of the composite sintered product.
  • the difference is no more than 10%.
  • the invention also extends to a method for preparing an alumina-zirconia composite powder which comprises dispersing a-alumina particles having an average particle size of from 0.1 ⁇ m to 2 ⁇ m in a zirconia sol having a zirconia dispersed phase having an average particle size of not larger than 0.1 ⁇ m, subjecting the resulting mixed dispersion to dehydration to obtain a dried mixture, and calcining the dried mixture to obtain a mixed powder of crystalline zirconia particles and a- alumina particles.
  • the dried mixture is preferably calcined at a temperature of from 500 to 1300°C.
  • the invention also extends to a method for making an alumina-zirconia composite sintered product which comprises shaping a mixed powder of crystalline zirconia particles and a-alumina particles obtained by the method of the invention and sintering the shaped powder to obtain an alumina-zirconia composite sintered product.
  • a sintered product obtained at a temperature of from 1300°C to 1600°C at normal pressure is subjected to hot isotactic pressing in an inert gas or in a mixed gas of oxygen and an inert gas at a temperature of from 1200 to 1600°C, provided that the treatment temperature is not higher than that used in the normal pressure sintering.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
EP19900314351 1989-12-28 1990-12-27 Alumina-zirconia composite sintered product and method for making the same Withdrawn EP0435677A3 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP338102/89 1989-12-28
JP33810289 1989-12-28
JP99197/90 1990-04-17
JP09919790A JP3198507B2 (ja) 1989-12-28 1990-04-17 アルミナ―ジルコニア複合焼結体
JP2100359A JP2803314B2 (ja) 1990-04-18 1990-04-18 アルミナ‐ジルコニア複合粉末および焼結体の製造方法
JP100359/90 1990-04-18

Publications (2)

Publication Number Publication Date
EP0435677A2 true EP0435677A2 (fr) 1991-07-03
EP0435677A3 EP0435677A3 (en) 1992-09-02

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EP (1) EP0435677A3 (fr)
AU (1) AU6847390A (fr)
CA (1) CA2033289A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007969A1 (fr) * 1992-09-25 1994-04-14 Minnesota Mining And Manufacturing Company Grains abrasifs contenant de l'oxyde de terres rares
US5429647A (en) * 1992-09-25 1995-07-04 Minnesota Mining And Manufacturing Company Method for making abrasive grain containing alumina and ceria
US5429648A (en) * 1993-09-23 1995-07-04 Norton Company Process for inducing porosity in an abrasive article
US5551963A (en) * 1992-09-25 1996-09-03 Minnesota Mining And Manufacturing Co. Abrasive grain containing alumina and zirconia
US5593467A (en) * 1993-11-12 1997-01-14 Minnesota Mining And Manufacturing Company Abrasive grain
US5645618A (en) * 1993-11-12 1997-07-08 Minnesota Mining And Manufacturing Company Method for making an abrasive article
EP0811586A2 (fr) * 1996-06-07 1997-12-10 Toray Industries, Inc. Matériau céramique composite pour milieux de pulvérisation et parties actives d'un broyeur pulvérisateur
EP1228774A1 (fr) * 2000-08-07 2002-08-07 Matsushita Electric Works, Ltd. Joint artificiel en ceramique composite de zircone-alumine
EP1514856A1 (fr) * 2003-09-10 2005-03-16 Kyocera Corporation Céramiques en alumine-zircone et leur procédé de fabrication.
US20080118722A1 (en) * 2005-01-27 2008-05-22 Kyocera Corporation Composite Ceramic and Method for Making the Same
US7608552B2 (en) * 2002-12-30 2009-10-27 Chemichl Ag Dental material or product and method of forming a dental product
DE102008044906A1 (de) 2008-08-29 2010-03-04 Ibu-Tec Advanced Materials Ag Verfahren zur Herstellung eines feinteiligen Pulverwerkstoffs sowie ein solcher Pulverwerkstoff
WO2011157494A1 (fr) 2010-06-17 2011-12-22 Evonik Degussa Gmbh Poudre composite à base de dioxyde de zirconium et d'oxyde d'aluminium et son procédé de préparation
WO2013105064A1 (fr) * 2012-01-13 2013-07-18 Patros S.R.L. Produit manufacturé pour la bijouterie et/ou l'orfèvrerie et/ou la bijouterie fantaisie, à base d'oxyde de zirconium et procédé pour sa réalisation
EP2735556A1 (fr) * 2011-07-19 2014-05-28 NGK Spark Plug Co., Ltd. Compact fritté et outil de coupe
WO2018010189A1 (fr) * 2016-07-14 2018-01-18 广东省材料与加工研究所 Particules céramiques à phases multiples à base de zro2-al2o3 résistantes à l'usure et procédé pour leur préparation et utilisation correspondante

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Publication number Priority date Publication date Assignee Title
AU683050B2 (en) * 1993-06-24 1997-10-30 Dentsply Gmbh Dental prosthesis
CN116922546B (zh) * 2023-09-18 2023-12-29 成都永益泵业股份有限公司 一种使用氧化锆制作成型件的方法及泵过流部件

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US4031177A (en) * 1969-10-31 1977-06-21 Compagnie Generale D'electroceramique Process for the manufacture of articles of translucent alumina
DE2717010A1 (de) * 1976-11-03 1978-05-18 Max Planck Gesellschaft Keramikformkoerper hoher bruchzaehigkeit
FR2546877A1 (fr) * 1977-10-05 1984-12-07 Feldmuehle Ag Materiau fritte
EP0141366A2 (fr) * 1983-10-26 1985-05-15 Carboloy Inc. Procédé de frittage accéléré pour céramiques
EP0397312A1 (fr) * 1989-05-12 1990-11-14 General Motors Corporation Frittage à basse température de zircone durci

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Publication number Priority date Publication date Assignee Title
US4031177A (en) * 1969-10-31 1977-06-21 Compagnie Generale D'electroceramique Process for the manufacture of articles of translucent alumina
DE2717010A1 (de) * 1976-11-03 1978-05-18 Max Planck Gesellschaft Keramikformkoerper hoher bruchzaehigkeit
FR2546877A1 (fr) * 1977-10-05 1984-12-07 Feldmuehle Ag Materiau fritte
EP0141366A2 (fr) * 1983-10-26 1985-05-15 Carboloy Inc. Procédé de frittage accéléré pour céramiques
EP0397312A1 (fr) * 1989-05-12 1990-11-14 General Motors Corporation Frittage à basse température de zircone durci

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007969A1 (fr) * 1992-09-25 1994-04-14 Minnesota Mining And Manufacturing Company Grains abrasifs contenant de l'oxyde de terres rares
US5429647A (en) * 1992-09-25 1995-07-04 Minnesota Mining And Manufacturing Company Method for making abrasive grain containing alumina and ceria
US5498269A (en) * 1992-09-25 1996-03-12 Minnesota Mining And Manufacturing Company Abrasive grain having rare earth oxide therein
US5551963A (en) * 1992-09-25 1996-09-03 Minnesota Mining And Manufacturing Co. Abrasive grain containing alumina and zirconia
US5429648A (en) * 1993-09-23 1995-07-04 Norton Company Process for inducing porosity in an abrasive article
US5593467A (en) * 1993-11-12 1997-01-14 Minnesota Mining And Manufacturing Company Abrasive grain
US5645618A (en) * 1993-11-12 1997-07-08 Minnesota Mining And Manufacturing Company Method for making an abrasive article
US5651801A (en) * 1993-11-12 1997-07-29 Minnesota Mining And Manufacturing Company Method for making an abrasive article
EP0811586A2 (fr) * 1996-06-07 1997-12-10 Toray Industries, Inc. Matériau céramique composite pour milieux de pulvérisation et parties actives d'un broyeur pulvérisateur
EP0811586A3 (fr) * 1996-06-07 1999-04-21 Toray Industries, Inc. Matériau céramique composite pour milieux de pulvérisation et parties actives d'un broyeur pulvérisateur
US5957398A (en) * 1996-06-07 1999-09-28 Toray Industries, Inc. Composite ceramic materials as a pulverization medium and for working parts of a pulverizer
KR100485278B1 (ko) * 1996-06-07 2005-08-23 도레이 가부시끼가이샤 분쇄기용 복합 세라믹으로 이루어지는 분쇄기 및 분쇄방법
EP1228774A4 (fr) * 2000-08-07 2004-03-17 Matsushita Electric Works Ltd Joint artificiel en ceramique composite de zircone-alumine
EP1228774A1 (fr) * 2000-08-07 2002-08-07 Matsushita Electric Works, Ltd. Joint artificiel en ceramique composite de zircone-alumine
US7608552B2 (en) * 2002-12-30 2009-10-27 Chemichl Ag Dental material or product and method of forming a dental product
EP1514856A1 (fr) * 2003-09-10 2005-03-16 Kyocera Corporation Céramiques en alumine-zircone et leur procédé de fabrication.
US20080118722A1 (en) * 2005-01-27 2008-05-22 Kyocera Corporation Composite Ceramic and Method for Making the Same
DE102008044906A1 (de) 2008-08-29 2010-03-04 Ibu-Tec Advanced Materials Ag Verfahren zur Herstellung eines feinteiligen Pulverwerkstoffs sowie ein solcher Pulverwerkstoff
EP2168936A1 (fr) 2008-08-29 2010-03-31 IBU-tec advanced materials AG Procédé de fabrication d'une matière active en poudre à fines particules et une telle matière active en poudre
WO2011157494A1 (fr) 2010-06-17 2011-12-22 Evonik Degussa Gmbh Poudre composite à base de dioxyde de zirconium et d'oxyde d'aluminium et son procédé de préparation
DE102010030216A1 (de) 2010-06-17 2011-12-22 Evonik Degussa Gmbh Zirkondioxid-Aluminiumoxid-Kompositpulver und Verfahren zu dessen Herstellung
EP2735556A1 (fr) * 2011-07-19 2014-05-28 NGK Spark Plug Co., Ltd. Compact fritté et outil de coupe
EP2735556A4 (fr) * 2011-07-19 2014-12-03 Ngk Spark Plug Co Compact fritté et outil de coupe
WO2013105064A1 (fr) * 2012-01-13 2013-07-18 Patros S.R.L. Produit manufacturé pour la bijouterie et/ou l'orfèvrerie et/ou la bijouterie fantaisie, à base d'oxyde de zirconium et procédé pour sa réalisation
WO2018010189A1 (fr) * 2016-07-14 2018-01-18 广东省材料与加工研究所 Particules céramiques à phases multiples à base de zro2-al2o3 résistantes à l'usure et procédé pour leur préparation et utilisation correspondante
AU2016415075B2 (en) * 2016-07-14 2020-08-20 Institute of Materials and Processing, Guangdong Academy of Sciences ZrO2-Al2O3 Multiphase Ceramic Particle for Wear-Resistance Application, Preparation Method Therefor and Use Thereof
AU2016415075B9 (en) * 2016-07-14 2021-01-28 Institute of Materials and Processing, Guangdong Academy of Sciences ZrO2-Al2O3 Multiphase Ceramic Particle for Wear-Resistance Application, Preparation Method Therefor and Use Thereof

Also Published As

Publication number Publication date
AU6847390A (en) 1991-07-04
CA2033289A1 (fr) 1991-06-29
EP0435677A3 (en) 1992-09-02

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